Method for filling recessed features in semiconductor devices with a low-resistivity metal

ABSTRACT

A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, and pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature, and removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature. The steps of pre-treating, depositing and removing may be repeated at least once to increase a thickness of the metal layer in the recessed feature.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Divisional of U.S. patent application Ser.No. 16/598,772, filed Oct. 10, 2019, currently granted as U.S. Pat. No.11,024,535, which claims the benefit of U.S. Provisional PatentApplication No. 62/744,038, filed on Oct. 10, 2018. All of theseapplications and patents are incorporated herein by reference, includingtheir specifications.

FIELD OF THE INVENTION

The present invention relates to semiconductor processing andsemiconductor devices, and more particularly, to a method for fillingrecessed features in semiconductor devices with a low-resistivity metal.

BACKGROUND OF THE INVENTION

Semiconductor devices contain filled recessed features such as trenchesor vias that are formed in a dielectric material such as an interlayerdielectric (ILD). Selective metal filling of the recessed features isproblematic due to finite metal deposition selectivity on a metal layerat the bottom of the recessed features relative to on the dielectricmaterial. This makes it difficult to fully fill the recessed featureswith a metal in a bottom-up deposition process before the on-set ofunwanted metal nuclei deposition on the field area (horizontal area)around the recessed features and on the sidewalls of the recessedfeatures.

SUMMARY OF THE INVENTION

Embodiments of the invention describe a method of filling recessedfeatures in semiconductor devices with a low-resistivity metal.According to one embodiment, the method includes providing a patternedsubstrate containing a recessed feature formed in a first layer and asecond layer that is exposed in the recessed feature, and pre-treatingthe substrate with a surface modifier that increases metal depositionselectivity on the second layer relative to on the first layer. Themethod further includes depositing a metal layer on the substrate byvapor phase deposition, where the metal layer is preferentiallydeposited on the second layer in the recessed feature, and removingmetal nuclei deposited on the first layer, including on a field area andon sidewalls of the first layer in the recessed feature, to selectivelyform the metal layer on the second layer in the recessed feature. Thesteps of pre-treating, depositing and removing may be repeated at leastonce to increase a thickness of the metal layer in the recessed feature.

According to another embodiment, the method includes providing apatterned substrate containing a recessed feature formed in a firstlayer and a second layer that is exposed in the recessed feature,depositing a metal-containing layer on the substrate, including in therecessed feature, and anisotropically removing the metal-containinglayer from a bottom of the recessed feature and from a field area aroundthe recessed feature to form the metal-containing layer on sidewalls ofthe recessed feature. The method further includes pre-treating thesubstrate with a surface modifier that increases metal depositionselectivity on the metal-containing layer on the sidewalls of therecessed feature and on the second layer relative to on the first layer,depositing a metal layer on the substrate by vapor phase deposition,where the metal layer is preferentially deposited on themetal-containing layer on the sidewalls and on the second layer in therecessed feature relative to on the field area around the recessedfeature, and removing metal nuclei deposited on the field area toselectively form the metal layer in the recessed feature. The steps ofpre-treating, depositing and removing may be repeated at least once toincrease a thickness of the metal layer in the recessed feature.

According to another embodiment, the method includes providing apatterned substrate containing a recessed feature formed in material,depositing a metal nitride layer on the substrate, including in therecessed feature and on a field area around the recessed feature, andoxidizing the metal nitride layer on the field area. The method furtherincludes depositing a metal layer on the substrate by vapor phasedeposition, where the metal layer is preferentially deposited on themetal nitride layer that is not oxidized in the recessed feature, andremoving metal nuclei deposited on the field area to selectively formthe metal layer in the recessed feature. The steps of depositing andremoving may be repeated at least once to increase a thickness of themetal layer in the recessed feature.

According to another embodiment, the method includes providing apatterned substrate containing a recessed feature formed in material,depositing a metal oxide layer on the substrate, including in therecessed feature and on a field area around the recessed feature,nitriding the metal oxide layer on the field area and in the recessedfeature, and oxidizing the nitrided metal oxide layer on the field area.The method further includes depositing a metal layer on the substrate byvapor phase deposition, where the metal layer is preferentiallydeposited on the nitrided metal oxide layer that is not oxidized in therecessed feature, and removing metal nuclei deposited on the field areato selectively form the metal layer in the recessed feature. The stepsof depositing and removing may be repeated at least once to increase athickness of the metal layer in the recessed feature.

According to another embodiment, the method includes providing apatterned substrate containing a recessed feature formed in material,depositing a metal oxide layer on the substrate, including in therecessed feature and on a field area around the recessed feature, andnitriding the metal oxide layer on the field area. The method furtherincludes depositing a metal layer on the substrate by vapor phasedeposition, where the metal layer is preferentially deposited on thenitrided metal oxide layer on the field area, and removing metal nucleideposited in the recessed feature to selectively form the metal layer onthe field area. The steps of depositing and removing may be repeated atleast once to increase a thickness of the metal layer in the recessedfeature.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconsidered in connection with the accompanying drawings, wherein:

FIGS. 1A-1F schematically show a method for selective metal formation ina recessed feature according to an embodiment of the invention;

FIGS. 2A-2E schematically show a method for selective metal formation ina recessed feature according to another embodiment of the invention;

FIGS. 3A-3E schematically show a method for selective metal formation ina recessed feature according to another embodiment of the invention;

FIGS. 4A-4F schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention;

FIGS. 5A-5E schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention;

FIGS. 6A-6D schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention;and

FIG. 7 shows a SEM image with selective Ru metal formation in recessedfeatures on a patterned substrate.

DETAILED DESCRIPTION OF SEVERAL EMBODIMENTS

Embodiments of the invention provide a method for selectively forming alow-resistivity metal in recessed features of a semiconductor device.The method can be used to fully fill the recessed features with thelow-resistivity metal. According to one embodiment, metal depositionselectivity by vapor phase deposition increases in the order:Si-containing material<metal-containing layer<metal. The deposited metalcan, for example, include Ru metal, Co metal, or W metal. An incubationtime for metal deposition is shortest on a metal and longest on aSi-containing material. An incubation time refers to a delay until metaldeposition starts on a surface during a deposition process. In oneembodiment, this may be used to preferentially form a metal in arecessed feature relative to on surfaces above the recessed feature. TheSi-containing material can include SiO₂, SiON, or SiN. The SiO₂ may bedeposited as a layer or formed by oxidation of Si, for example byexposure to air, oxygen (O₂ or O), ozone, or H₂O. The SiN may bedeposited as a layer or formed by nitridation of Si, for example byexposure to N or NH₃. The SiON may be deposited as a layer or formed bynitriding SiO₂, by oxidation of SiN, or by oxidation and nitridation ofSi. The metal-containing layer can include a metal oxide, a metalnitride, a metal carbide, a metal silicide, a metal sulfide, or a metalphosphide. The metal silicide may be formed by metal deposition on Si orSi deposition on a metal, followed by a heat-treatment, or by formationof the metal silicide during a deposition process. The metal can, forexample, include Ru metal, Co metal, or W metal.

FIGS. 1A-1F schematically shows a method for selective metal formationin a recessed feature according to an embodiment of the invention. Themetal can, for example, be selected from the group consisting of Rumetal, Co metal, and W metal. The patterned substrate 1 contains a fieldarea 101 around a recessed feature 110 formed in a first layer 100. Therecessed feature 110 contains sidewalls 103 and a second layer 102 thathas an exposed surface 104.

According to one embodiment, the first layer 100 can include adielectric material and the second layer 102 can include a metal layer.The dielectric material can, for example, contain SiO₂, a low dielectricconstant (low-k) material such as fluorinated silicon glass (FSG),carbon doped oxide, a polymer, a SiCOH-containing low-k material, anon-porous low-k material, a porous low-k material, a CVD low-kmaterial, a spin-on dielectric (SOD) low-k material, or any othersuitable dielectric material, including a high dielectric constant(high-k) material. In some examples, a width (critical dimension (CD))of the recessed feature 110 can be between about 10 nm and about 100 nm,between about 10 nm and about 15 nm, between about 20 nm and about 90,or between about 40 nm and about 80 nm. In some examples, the depth ofthe recessed feature 110 can between bout 40 nm and about 200 nm, orbetween about 50 nm and about 150 nm. In some examples, and the recessedfeature 110 can have an aspect ratio (depth/width) between about 2 andabout 20, or between about 4 and about 6. The second layer 102 caninclude a low-resistivity metal such as Cu metal, Ru metal, Co metal, Wmetal, or a combination thereof. In one example, the second layer 102can include two or more stacked metal layers. Examples of the stackedmetal layers include Co metal on Cu metal (Co/Cu) and Ru metal on Cumetal (Ru/Cu).

The method includes pre-treating the patterned substrate 1 with asurface modifier that adsorbs on the first layer 100 and therebyincreases metal deposition selectivity on the second layer 102 relativeto on the first layer 100, including on the sidewalls 103 and on thefield area 101. The presence of the surface modifier hinders depositionof the metal layer on first layer 100 but the second layer 102 is notmodified. According to one embodiment, the patterned substrate 1 ispre-treated with a surface modifier by exposure to a reactant gas thatcontains a molecule that is capable of forming self-assembled monolayers(SAMs) on a substrate. SAMs are molecular assemblies that are formedspontaneously on substrate surfaces by adsorption and are organized intomore or less large ordered domains. The SAMs can include a molecule thatpossesses a head group, a tail group, and a functional end group, andSAMs are created by the chemisorption of head groups onto the substratefrom the vapor phase at room temperature or above room temperature,followed by a slow organization of the tail groups. Initially, at smallmolecular density on the surface, adsorbate molecules form either adisordered mass of molecules or form an ordered two-dimensional “lyingdown phase”, and at higher molecular coverage, over a period of minutesto hours, begin to form three-dimensional crystalline or semicrystallinestructures on the substrate surface. The head groups assemble togetheron the substrate, while the tail groups assemble far from the substrate.According to one embodiment, the head group of the molecule forming theSAMs can include a thiol, a silane, or a phosphonate. Examples ofsilanes include molecule that include C, H, Cl, F, and Si atoms, or C,H, Cl, and Si atoms. Non-limiting examples of the molecule includeperfluorodecyltrichlorosilane (CF₃(CF₂)₇CH₂CH₂SiCl₃),perfluorodecanethiol (CF₃(CF₂)₇CH₂CH₂SH), chlorodecyldimethylsilane(CH₃(CH₂)₈CH₂Si(CH₃)₂Cl), and tertbutyl(chloro)dimethylsilane((CH₃)₃CSi(CH₃)₂Cl)).

According to some embodiments of the invention, the reactant gas cancontain a silicon-containing gas, including an alkyl silane, analkoxysilane, an alkyl alkoxysilane, an alkyl siloxane, analkoxysiloxane, an alkyl alkoxysiloxane, an aryl silane, an acyl silane,an aryl siloxane, an acyl siloxane, a silazane, or any combinationthereof. According to some embodiments of the invention, the reactantgas may be selected from dimethylsilane dimethylamine (DMSDMA),trimethylsilane dimethylamine (TMSDMA), bis(dimethylamino)dimethylsilane (BDMADMS), and other alkyl amine silanes. According toother embodiments, the reactant gas may be selected from N,Obistrimethylsilyltrifluoroacetamide (BSTFA) and trimethylsilyl-pyrrole(TMS-pyrrole).

According to some embodiments of the invention, the reactant gas may beselected from silazane compounds. Silazanes are saturatedsilicon-nitrogen hydrides. They are analogous in structure to siloxaneswith —NH— replacing —O—. An organic silazane precursor can furthercontain at least one alkyl group bonded to the Si atom(s). The alkylgroup can, for example, be a methyl group, an ethyl group, a propylgroup, or a butyl group, or combinations thereof. Furthermore, the alkylgroup can be a cyclic hydrocarbon group such as a phenyl group. Inaddition, the alkyl group can be a vinyl group. Disilazanes arecompounds having from 1 to 6 methyl groups attached to the silicon atomsor having 1 to 6 ethyl groups attached the silicon atoms, or adisilazane molecule having a combination of methyl and ethyl groupsattached to the silicon atoms.

The method further includes depositing a metal layer 106 a on thepatterned substrate 1 by vapor phase deposition, where the metal layer106 a is preferentially deposited on the second layer 102 in therecessed feature 110. The metal layer 106 a can, for example, beselected from the group consisting of Ru metal, Co metal, and W metal.According to one embodiment of the invention, Ru metal may be depositedby chemical vapor phase deposition (CVD) or atomic layer deposition(ALD). Examples of Ru-containing precursors include Ru₃(CO)₁₂,(2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium(Ru(DMPD)(EtCp)), bis(2,4-dimethylpentadienyl) ruthenium (Ru(DMPD)₂),4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium(Ru(DMPD)(MeCp)), and bis(ethylcyclopentadienyl) ruthenium (Ru(EtCp)₂),as well as combinations of these and other precursors.

As schematically shown in FIG. 1B, the metal deposition may not becompletely selective and metal nuclei 107 a may be deposited on thesidewalls 103 and on the field area 101. Unlike the metal layer 106 a,the metal nuclei 107 a may be form a non-continuous layer where thetotal amount of the metal in the metal nuclei 107 a is less than theamount of the metal in the metal layer 106 a.

In one example, Ru metal was deposited by CVD using a Ru₃(CO)₁₂precursor in a CO carrier gas. After pre-treating the substrate with asurface modifier, Ru metal nuclei were observed on a dielectric materialafter a thickness of about 15-20 nm of Ru metal was deposited on a Cumetal layer at a bottom of a recessed feature in the dielectricmaterial. This illustrates the limited selectivity of Ru metaldeposition on different materials and the difficulty of selectivelydepositing and filling recessed features deeper than about 15-20 nm withRu metal before the onset of Ru metal deposition on dielectric surfaces.Ru metal deposition rates by CVD were observed to decrease in the order:metal>metal nitride or nitride metal oxide>metal oxide or oxidized metalnitride>ILD, where the Ru metal deposition rate is highest on a metalsurface and lowest on an ILD surface. This may be utilized forpreferential Ru metal deposition on the different materials. ILDsinclude dielectric compounds that contain silicon, carbon, or bothsilicon and carbon. Examples include SiO₂, SiON, SiN, SiCOH, Si, SiC,and C.

The method further includes removing the metal nuclei 107 a from thepatterned substrate 1 to selectively form the metal layer 106 a on thesecond layer 102 in the recessed feature 110. This is schematicallyshown in FIG. 1C. It is may be preferable that the removal of the metalnuclei 107 a be performed before they get too big and are more difficultto remove efficiently. In one example, Ru metal nuclei 107 a may beremoved by etching using reactive ion etching (ME), for example usingplasma-excited O₂ gas and optionally adding a halogen-containing gas(e.g., Cl₂).

The steps of pre-treating, depositing and removing may be repeated atleast once to increase a thickness of the metal deposited in therecessed feature 110. This is schematically shown in FIG. 1D whereadditional metal layer 106 b is preferentially deposited on the metallayer 106 a and additional metal nuclei 107 b are deposited on thesidewalls 103 and on the field area 101. Thereafter, as shown in FIG.1E, the additional metal nuclei 107 b are removed. In one example, thepre-treating, depositing and removing may be repeated until the recessedfeature 110 is fully filled with the metal. This is schematically shownin FIG. 1F, where the recessed feature 110 is filled with metal layers106 a-106 c.

A process example for selective Ru metal formation in a recessed featureincludes a pre-treatment using a TMSDMA gas exposure where TMSDMA liquidis vaporized and diluted with N₂ gas, a substrate temperature betweenabout 180° C. and about 250° C., a process chamber pressure of about 5Torr, and a 10 sec exposure time with no plasma excitation. A Ru metalCVD process includes a process gas containing Ru₃(CO)₁₂+CO (e.g., a gasflow ratio of about 1:100), a substrate temperature between about 135°C. and about 180° C. (for example about 160° C.), a process chamberpressure between about 1 mTorr and about 20 mTorr (for example about 5mTorr), and a 400 sec exposure without plasma excitation that depositsabout 20 nm of Ru metal on a metal surface. A Ru metal removal processincludes the use of an etching gas of containing O₂ and Cl₂ (e.g., a gasflow ratio of about 100:1), a substrate temperature between about roomtemperature and about 370° C. (for example about 370° C.), plasmaexcitation using a capacitively coupled plasma source with about 1200 Wof RF power applied to a top electrode and between about OW and about300 W (for example OW) of RF power applied to a bottom electrode(substrate holder), a process chamber pressure of about 5 mTorr, and a40 sec exposure time to remove the equivalent of about 5 nm of Ru metalnuclei.

FIG. 7 shows a SEM image with selective Ru metal formation in recessedfeatures on a patterned substrate. The as-received patterned substratecontained raised SiO₂ features on a W metal film. The raised SiO₂features were about 113 nm tall, about 31 nm wide, and were spaced apartby about 87 nm. The raised SiO₂ features formed recessed features thatwere about 113 nm deep and with a width of about 87 nm. The figure showsthe results following a deposition process that included pre-treatingthe patterned substrate with a surface modifier containing TMSDMA, a Rumetal CVD deposition step using Ru₃(CO)₁₂+CO, and a Ru metal etchingstep using plasma-excited O₂ gas+Cl₂ gas that removed Ru metal nucleifrom the sidewalls of the recessed features. The sequence ofpre-treating, Ru metal depositing, and Ru metal nuclei removal wasperformed four times. The figure illustrates that Ru metal wasselectively formed in the recessed features and no Ru metal nuclei werepresent on the sidewalls of the recessed features or on the top surfacesof the etched SiO₂ features. The thickness of the Ru metal formed in therecessed features was about 69 nm and filled about 61% of the volume ofthe recessed features.

FIGS. 2A-2F schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention.FIG. 1A has been reproduced as patterned substrate 2 in FIG. 2A. Themethod includes providing the patterned substrate 2 containing arecessed feature 110 formed in a first layer 100 and a second layer 102that is exposed in the recessed feature 110. As shown in FIG. 2B, themethod includes depositing a metal-containing layer 111 on the patternedsubstrate 2, including in the recessed feature 110 and on the field area101 around the recessed feature 110. The metal-containing layer 111 maybe conformal and in some examples, the metal-containing layer 111 caninclude a metal oxide, a metal nitride, or a combination thereof. Themetal oxide can, for example, include Al₂O₃, TiO₂, HfO₂, or MnO₂, andthe metal nitride can, for example, include AlN, TiN, HfN, or MnN.

Thereafter, as shown in FIG. 2C, the method further includesanisotropically removing the metal-containing layer 111 from a bottom ofthe recessed feature 110 and from the field area 101 around the recessedfeature 110 to form the metal-containing layer 111 on the sidewalls 103of the recessed feature 110. The method further includes pre-treatingthe patterned substrate 2 with a surface modifier that that adsorbs onthe first layer 100, including on the field area 101, and therebyincreases metal deposition selectivity on the metal-containing layer 111on the sidewalls 103 of the recessed feature 110 and on the second layer102 relative to on the first layer 100.

The method further includes depositing a metal layer 112 on thepatterned substrate 2 by vapor phase deposition, where the metal layer112 is preferentially deposited on the metal-containing layer 111 on thesidewalls 103 and on the second layer 102 at the bottom of the recessedfeature 110, relative to on the field area 101 around the recessedfeature 110. The metal layer 112 can, for example, be selected from thegroup consisting of Ru metal, Co metal, and W metal. As schematicallyshown in FIG. 2D, the metal deposition may not be completely selectiveand metal nuclei 113 may be deposited on the field area 101. Unlike themetal layer 112, the metal nuclei 113 may be form a non-continuous layerwhere the total amount of the metal in the metal nuclei 113 is less thanthe amount of the metal in the metal layer 112. According to theembodiment shown in FIG. 2D, the metal layer 112 may fully fill therecessed feature 110. As shown in FIG. 2E, the method further includesremoving the metal nuclei 113 deposited on the field area 101 of thefirst layer 100 around the recessed feature 110 to selectively form themetal layer 112 in the recessed feature 110.

According to another embodiment, the metal layer 112 may not fully fillthe recessed feature 110, and the pre-treating, depositing and removingmay be repeated at least once to increase a thickness of the metaldeposited in the recessed feature 110. According to one embodiment, thepre-treating, depositing and removing may be repeated until the recessedfeature 110 is fully filled with the metal.

FIGS. 3A-3E schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention.FIG. 1A has been reproduced as patterned substrate 3 in FIG. 3A. Themethod includes providing the patterned substrate 3 containing arecessed feature 110 formed in a material. In one example, the materialcan include a first layer 100 and a second layer 102 that is exposed inthe recessed feature 110. As shown in FIG. 3B, the method furtherincludes depositing a metal nitride layer 114 on the patterned substrate3, including in the recessed feature 110 and on the field area 101around the recessed feature 110. The metal nitride layer 114 may beconformal, and in some examples, the metal nitride layer 114 can includeAlN, TiN, HfN, or MnN.

Thereafter, the method further includes oxidizing the metal nitridelayer 114 on the field area 101 to form an oxidized metal nitride layer115. As used herein, the oxidizing process incorporates oxygen into atleast a surface region of the metal nitride layer 114. As schematicallyshown in FIG. 3C, the metal nitride layer 114 may also be oxidized inthe recessed feature 110 near the opening of the recessed feature 110.The step of oxidizing the metal nitride layer 114 can be performed usingplasma-excited O₂ gas, where the small opening of the recessed feature110 limits the penetration of the plasma-excited O₂ gas into therecessed feature 110. This limits the oxidation of the metal nitridelayer 114 to the field area 101 and an upper portion of the recessedfeature 110.

The method further includes depositing a metal layer 116 on thesubstrate by vapor phase deposition, where the metal layer 116 ispreferentially deposited on the metal nitride layer 114 that is notoxidized in the recessed feature 110. The preferential metal depositionis believed to be due to a shorter incubation time for the metaldeposition on the metal nitride layer 114 relative to on the oxidizedmetal nitride layer 115. As schematically shown in FIG. 3D, the metaldeposition may not be completely selective and metal nuclei 123 may bedeposited on the field area 101. Unlike the metal layer 116, the metalnuclei 123 may be form a non-continuous layer where the total amount ofthe metal in the metal nuclei 123 is less than the amount of the metalin the metal layer 116.

According to the embodiment shown in FIG. 3D, the metal layer 116 mayfully fill the recessed feature 110 where oxidation of the metal nitridelayer 114 is avoided. As shown in FIG. 3E, the method further includesremoving the metal nuclei 123 deposited on the field area 101 of thefirst layer 100 around the recessed feature 110 to selectively form themetal layer 116 in the recessed feature 110.

According to another embodiment, the metal layer 116 may not fully fillthe recessed feature 110 where oxidation of the metal nitride layer 114is avoided, and the steps of depositing and removing may be repeated atleast once to increase a thickness of the metal layer 116 deposited inthe recessed feature 110. According to one embodiment, the steps ofdepositing and removing may be repeated until the recessed feature 110is fully filled with the metal layer 116.

FIGS. 4A-4F schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention.FIG. 1A has been reproduced as patterned substrate 4 in FIG. 4A. Themethod includes providing the patterned substrate 4 containing arecessed feature 110 formed in a material. In one example, the materialcan include a first layer 100 and a second layer 102 that is exposed inthe recessed feature 110. As shown in FIG. 4B, the method furtherincludes depositing a metal oxide layer 117 on the patterned substrate4, including in the recessed feature 110 and on the field area 101around the recessed feature 110. The metal oxide layer 117 may beconformal, and in some examples, the metal oxide layer 117 can includeAl₂O₃, TiO₂, HfO₂, or MnO₂.

Thereafter, the method further includes nitriding the metal oxide layer117 on the field area 101 and in the recessed feature 110 to form anitrided metal oxide layer 118. As used herein, the nitriding processincorporates nitrogen into at least a surface region of the metal oxidelayer 117. As schematically shown in FIG. 4C, the nitrided metal oxidelayer 118 may be conformal. The step of nitriding the metal oxide layer117 may be carried out using a thermal nitriding process (e.g., NH₃anneal in the absence of a plasma) that effectively nitrides at least aportion of the thickness of the entire metal oxide layer 117, includingin the recessed feature 110.

Thereafter, the method further includes oxidizing the nitrided metaloxide layer 118 on the field area 101 to form an oxidized nitrided metaloxide layer 119. As used herein, the oxidizing process incorporatesoxygen into at least a surface region of the nitrided metal oxide layer118. The step of oxidizing the nitrated metal oxide layer can beperformed using plasma-excited O₂ gas, where the small opening of therecessed feature 110 limits the penetration of the plasma-excited O₂ gasinto the recessed feature 110. This limits the oxidation of the nitritedmetal oxide layer to the field area 101 and an upper portion of therecessed feature 110. This is schematically shown in FIG. 4D.

The method further includes depositing a metal layer 120 on thepatterned substrate 4 by vapor phase deposition, where the metal layer120 is preferentially deposited on the nitrided metal oxide layer 118that is not oxidized in the recessed feature 110. The preferential metaldeposition is believed to be due to a shorter incubation time for themetal deposition on the nitrated metal oxide layer relative to on theoxidized nitrided metal oxide layer 119.

As schematically shown in FIG. 4E, the metal deposition may not becompletely selective and metal nuclei 121 may be deposited on theoxidized nitrided metal oxide layer 119 on the field area 101. Unlikethe metal layer 120, the metal nuclei 121 may be form a non-continuouslayer where the total amount of the metal in the metal nuclei 121 isless than the amount of the metal in the metal layer 120.

According to the embodiment shown in FIG. 4E, the metal layer 120 mayfully fill the recessed feature 110 where oxidation of the nitridedmetal oxide layer 118 is avoided. As shown in FIG. 4F, the methodfurther includes removing the metal nuclei 121 deposited on the fieldarea 101 of the first layer 100 around the recessed feature 110 toselectively form the metal layer 120 in the recessed feature 110.

According to another embodiment, the metal layer 120 may not fully fillthe recessed feature 110 where oxidation of the nitrided metal oxidelayer 118 is avoided, and the steps of depositing and removing may berepeated at least once to increase a thickness of the metal layer 120deposited in the recessed feature 110. According to one embodiment, thesteps of depositing and removing may be repeated until the recessedfeature 110 is fully filled with the metal layer 120.

FIGS. 5A-5D schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention.FIG. 5A shows a patterned substrate 5 containing recessed features 510formed in a material 500, where the recessed features contain sidewalls503 and bottom 502. The method includes depositing a metal oxide layer504 on the patterned substrate 5, including in the recessed features 510and on a field area 501 around the recessed features 510. This isschematically shown in FIG. 5B.

The method further includes nitriding the metal oxide layer 504 on thefield area 101. As used herein, the nitriding process incorporatesnitrogen into at least a surface region of the metal oxide layer 504 toform a nitrided metal oxide layer 505. This is schematically shown inFIG. 5C. The step of nitriding the metal oxide layer 504 can beperformed using plasma-excited nitrogen-containing gas (e.g., N₂ orNH₃), where the small openings of the recessed features 510 limit thepenetration of the plasma-excited nitrogen-containing gas into therecessed features 510.

The method further includes depositing a metal layer 506 on thepatterned substrate 5 by vapor phase deposition, where the metal layer506 is preferentially deposited on the nitrided metal oxide layer 505 onthe field area 501. As schematically shown in FIG. 5D, the metaldeposition may not be completely selective and metal nuclei 507 may bedeposited on the metal oxide layer 504 in the recessed features 510.

The method further includes removing the metal nuclei 507 deposited inthe recessed features 510 to selectively form the metal layer 506 on thefield area 501. This is schematically shown in FIG. 5E. The steps ofdepositing and removing may be repeated at least once to increase athickness of the metal layer 506 on the field area 501.

FIGS. 6A-6D schematically shows a method for selective metal formationin a recessed feature according to another embodiment of the invention.In one example, shown in FIG. 6A, the patterned substrate 6 may includea portion of a 3D NAND device. The method include providing a patternedsubstrate 6 containing an etched vertical feature 610 and etchedhorizontal features 601 in a material 600. The etched vertical feature610 may be tapered with a larger opening near the top than near thebottom. In one example, the material 600 may include SiO₂ or SiN. Themethod further includes nitriding the etched vertical feature 610 andthe etched horizontal features 601 to form a nitrided layer 602. Theprocess of nitriding can include a thermal nitriding process (e.g., NH₃anneal in the absence of a plasma) that nitrides both the etchedvertical feature 610 and etched horizontal features 601. Thereafter, themethod includes a plasma treatment (e.g., an Ar plasma) that removes thenitrided layer 602 from the etched vertical feature 610, while retainingthe nitrided layer 602 in the etched horizontal features 601. Theresulting patterned substrate 6 is shown in FIG. 6B. The method furtherincludes depositing a metal layer 603 on the patterned substrate 6 byvapor phase deposition, where the metal layer 603 is preferentiallydeposited on the nitrided layer 602 in the etched horizontal features601 relative to on the etched vertical feature 610. This is shown inFIG. 6C. The vapor phase deposition is performed until the etchedvertical feature 610 is also fully filled with a metal layer 604. Theselective metal deposition is due to a higher metal deposition rate onthe nitrided layer 602 than on the etched vertical feature 610 that isnot nitrided. This allows for complete metal filling of the etchedvertical feature 610 and the etched horizontal features 601 without anyvoids.

A method for filling recessed features in semiconductor devices with alow-resistivity metal has been disclosed in various embodiments. Theforegoing description of the embodiments of the invention has beenpresented for the purposes of illustration and description. It is notintended to be exhaustive or to limit the invention to the precise formsdisclosed. This description and the claims following include terms thatare used for descriptive purposes only and are not to be construed aslimiting. Persons skilled in the relevant art can appreciate that manymodifications and variations are possible in light of the aboveteaching. Persons skilled in the art will recognize various equivalentcombinations and substitutions for various components shown in theFigures. It is therefore intended that the scope of the invention belimited not by this detailed description, but rather by the claimsappended hereto.

What is claimed is:
 1. A method of forming a semiconductor device, themethod comprising: providing a patterned substrate containing a recessedfeature formed in a first layer and a second layer that is exposed inthe recessed feature; depositing a metal-containing layer on thepatterned substrate, including in the recessed feature; anisotropicallyremoving the metal-containing layer from a bottom of the recessedfeature and from a field area around the recessed feature to form themetal-containing layer on sidewalls of the recessed feature;pre-treating the patterned substrate with a surface modifier thatincreases metal deposition selectivity on the metal-containing layer onthe sidewalls of the recessed feature and on the second layer relativeto on the first layer; depositing a metal layer on the patternedsubstrate by vapor phase deposition, where the metal layer ispreferentially deposited on the metal-containing layer on the sidewallsand on the second layer in the recessed feature, relative to on thefield area around the recessed feature; and removing metal nucleideposited on the field area to selectively form the metal layer in therecessed feature.
 2. The method of claim 1, further comprising:repeating the pre-treating, depositing and removing at least once toincrease a thickness of the metal layer in the recessed feature.
 3. Themethod of claim 1, wherein the pre-treating includes formingself-assembled monolayers (SAMs) on the second layer.
 4. The method ofclaim 1, wherein the metal layer is selected from the group consistingof Ru metal, Co metal, and W metal, and the second layer is selectedfrom the group consisting of Cu metal, Ru metal, Co metal, W metal, anda combination thereof.
 5. The method of claim 1, wherein themetal-containing layer contains a metal oxide, a metal nitride, or acombination thereof.
 6. The method of claim 1, wherein the metal oxideincludes Al₂O₃, TiO₂, HfO₂, or MnO₂, and the metal nitride includes AlN,TiN, HfN, or MnN.
 7. The method of claim 1, wherein the first layerincludes a dielectric material and the second layer includes an initialmetal layer.
 8. The method of claim 1, wherein the pre-treating includesexposing the patterned substrate to a silicon-containing gas.
 9. Themethod of claim 8, wherein the silicon-containing gas includes an alkylsilane, an alkoxysilane, an alkyl alkoxysilane, an alkyl siloxane, analkoxysiloxane, an alkyl alkoxysiloxane, an aryl silane, an acyl silane,an aryl siloxane, an acyl siloxane, a silazane, or combination thereof.10. The method of claim 8, wherein the silicon-containing gas includesdimethylsilane dimethylamine (DMSDMA), trimethylsilane dimethylamine(TMSDMA), or bis(dimethylamino) dimethylsilane (BDMADMS).
 11. The methodof claim 8, wherein the silicon-containing gas includesN,O-bistrimethylsilyltrifluoroacetamide (BSTFA) ortrimethylsilyl-pyrrole (TMS-pyrrole).
 12. The method of claim 1, whereinthe removing includes reactive ion etching (RIE).
 13. The method ofclaim 1, wherein the removing includes exposing the patterned substrateto plasma-excited etching gas containing O₂ gas and optionally ahalogen-containing gas.
 14. A method of forming a semiconductor device,the method comprising: providing a patterned substrate containing arecessed feature formed in a first layer containing a dielectricmaterial and a second layer containing an initial metal layer that isexposed in the recessed feature; depositing a metal-containing layer onthe patterned substrate, including in the recessed feature;anisotropically removing the metal-containing layer from a bottom of therecessed feature and from a field area around the recessed feature toform the metal-containing layer on sidewalls of the recessed feature;pre-treating the patterned substrate with a surface modifier thatincreases metal deposition selectivity on the metal-containing layer onthe sidewalls of the recessed feature and on the second layer relativeto on the first layer, wherein the pre-treating includes exposing thepatterned substrate to a silicon-containing gas; depositing a ruthenium(Ru) metal layer on the patterned substrate by vapor phase depositionusing a gaseous exposure of a Ru-containing precursor, where the Rumetal layer is preferentially deposited on the metal-containing layer onthe sidewalls and on the second layer in the recessed feature, relativeto on the field area around the recessed feature; and removing Ru metalnuclei deposited on the field area to selectively form the Ru metallayer in the recessed feature.
 15. The method of claim 14, furthercomprising: repeating the pre-treating, depositing and removing at leastonce to increase a thickness of the Ru metal layer in the recessedfeature.
 16. The method of claim 14, wherein the pre-treating includesforming self-assembled monolayers (SAMs) on the second layer.
 17. Themethod of claim 14, wherein the metal-containing layer contains a metaloxide, a metal nitride, or a combination thereof.
 18. The method ofclaim 17, wherein the metal oxide includes Al₂O₃, TiO₂, HfO₂, or MnO₂,and the metal nitride includes AlN, TiN, HfN, or MnN.
 19. The method ofclaim 14, wherein the silicon-containing gas includes an alkyl silane,an alkoxysilane, an alkyl alkoxysilane, an alkyl siloxane, analkoxysiloxane, an alkyl alkoxysiloxane, an aryl silane, an acyl silane,an aryl siloxane, an acyl siloxane, a silazane, or combination thereof.20. A method of forming a semiconductor device, the method comprising:providing a patterned substrate containing a recessed feature formed ina first layer containing a dielectric material and a second layercontaining an initial metal layer that is exposed in the recessedfeature; depositing a metal-containing layer on the patterned substrate,including in the recessed feature; anisotropically removing themetal-containing layer from a bottom of the recessed feature and from afield area around the recessed feature to form the metal-containinglayer on sidewalls of the recessed feature; pre-treating the patternedsubstrate with a surface modifier that increases metal depositionselectivity on the metal-containing layer on the sidewalls of therecessed feature and on the second layer relative to on the first layer,wherein the pre-treating includes exposing the patterned substrate to asilicon-containing gas; depositing a ruthenium (Ru) metal layer on thepatterned substrate by vapor phase deposition using a gaseous exposureof a Ru-containing precursor, wherein depositing the ruthenium (Ru)metal layer includes exposing the patterned substrate to Ru₃(CO)₁₂ andcarbon monoxide (CO), and wherein the Ru metal layer is preferentiallydeposited on the metal-containing layer on the sidewalls and on thesecond layer in the recessed feature, relative to on the field areaaround the recessed feature; removing Ru metal nuclei deposited on thefield area to selectively form the Ru metal layer in the recessedfeature; and repeating the pre-treating, depositing and removing atleast once to increase a thickness of the Ru metal layer in the recessedfeature.